N-thiotrichloromethyl morpholine and fungicidal compositions containing same



Patented May 22, 1951 N-THIOTRICHLOROMETHYL MORPHOLINE AND FUNGICIDALCOMPOSITIONS CON- TAININ G SAME Roger S. Hawley, Linden, N. J assignorto Standard Oil Development Company, a corporation of Delaware NoDrawing. Application June 11, 1949, Serial No. 98,621

8 Claims.

This invention relates to new and useful improvements in parasiticidalpreparations and more particularly to improved fungicides, insecticides,and germicicles. This invention also relates to methods of protectingorganic material subject to attack by low orders of organisms. Thisinvention further relates to the synthesis of a new chemical compound,N-thiotrichloromethyl morpholine corresponding to the formula:

O NSCCla U. S. applications, Serial Nos. 773,925, filed September 13,1947 now abandoned, and 90,271, filed April 28, 1949, discloseN-thiotrichloromethyl imides of dicarboxylic acids as activeparasiticides.

It has now been found that N-thiotrichloromethyl derivatives ofheterocyclic nitrogen containing rings and particularlyN-thiotrichloromethyl morpholine are extremely effective for checkingthe growth of bacteria, fungi, and insects. These compounds may thus beused as novel ingredients of seed and plant protectants because of theirdisinfecting action on soil containing harmful organisms.

Suitable compounds of the indicated type are thus illustrated by FormulaI below:

CH2CH2 NSC C1 Egg-Oz Formula I whereX is a radical selected from thegroup consisting of O, S-, and CH2. Substituted nuclear derivatives ofthese compounds may also be used, as the NS C013 portion of thecompounds is believed to be the physiologically potent group. Thenuclear substituted groups thus may be alkyl, halogen, and similargroups.

The novel N-thiotrichloromethyl heterocyclic compounds of this inventionmay be prepared in general by the reaction of perchloromethylmercaptan(CISCCls) with the corresponding nitrogen containing heterocycliccompound. Formula II illustrates this reaction between morpholine andperchloromethylmercaptan.

OH OH 2 O NH (318001 CH2O 2 CHr-CH;

E01 O NSOGla CHz-C 2 Formula II The preparation of the morpholinestarting material is known in the art and is not the subject of thisinvention and therefore has not been here described.

N-thiotrichloromethyl morpholine can be prepared in general by firstdissolving the morpholine in Water. lhe mixture is then stirred and thetemperature kept below about C. An approximately equal quantity ofperchloromethylmercaptan is added over a period of about one hour. Thereaction is continued for about an hour after all the mercaptan has beenadded. After cooling, the reaction mixture is filtered to remove theN-thiotrichloromethyl morpholine product which has precipitated out.

The N thiotrichloromethyl morpholine can also be prepared in an organicsolvent such as benzene o1" dioxane. The reaction is conducted asdiscussed in the preceding paragraph. The morpholine hydrochloride isrelatively insoluble in the organic solvent and separates out and can bereused as feed material. The N-thiotrichloromethyl morpholine, which ismore soluble in the organic solvent, is then crystallized therefrom byconcentration of the solvent. If insufiici'ent solvent is used todissolve all the N-thiotrichloromethyl morpholine, some will precipitateout and can be separated from the morpholine hydrochloride by waterwashing out the morpholine hydrochloride or by extracting theN-thiotrichloromethyl morpholine with more organic solvent.

The following examples are given to illustrate this invention andinclude both the preparation of N-thiotrichloromethyl morpholine whichis made from the cheap and readily available morpholine, and testresults obtained on its use as a fungicide.

EXAMPLE I Preparation of N thz'otrichloromethyl morpholine To a 2-liter,S-neck flask equipped with a stirrer, condenser, thermometer, anddropping funnel, was added 26.1 gms. (0.3 mol) of morpholine and about200 cc. of benzene. 55.8gms. (0.3 mol) of perchloromethylmercaptan wasadded dropwise with stirring. It was necessary to add more benzene (700cc.) during the addition of perchloromethylmercaptan on account of theprecipitate formed. The addition of perchloromethylmercaptan took about45 minutes and the temperature did not rise above 40 C. Stirring wascontinued about one hour after all the perchloromethylmercaptan had beenadded. The mixture was allowed to stand overnight and then cooled andfiltered. The white precipitate was washed with petroleum ether on aBuchner funnel, filtered, and dried. Yield20.0 gms. of morpholinehydrochloride containing some N-thiotrichloromethyl morpholine. Thefiltrate was concentrated on a steam bath with reduced pressure and theresidue on cooling solidified, giving needle-like crystals. The crystalswere washed twice with a small amount of cold petroleum ether, filtered,and air dried. 21 gms. were obtained of white crystalline material,which is somewhat soluble in petroleum ether. About 10 gms. more wereobtained on evaporating off the petroleum ether from the filtrate fromthe petroleum ether washings of the final product. Analysis of a sampleof the 21 gms. of the white crystalline product-N-thiotrichloromethylmorpholine gave 25.37% C, 44.39% 012, and 13.46% S. Theoretical: 25.38%C, 44.97% C12 and 13.55% S. The melting point was 8687 C.

EXAMPLE II N-thiotricnloromethyl morpholine was tested for fungicidalactivity.

The Slide Germination Technique for fungicidal testing was carried outas described by Wellman and McCallan (Contributions of Boyce ThompsonInstitute, vol. 3, No. 3, pages 171-176). Against Alternaria solam' andScleroti'm'a fructicola, the fungicidal inhibiting concentration was inthe range of from .01% to 001% and 0.001% to 0.0001%, respectively.These figures are concentrations of test compound in per cent to give anLD50.

The new compounds of this invention may thus be applied to parentmaterials to retard or prevent fungus growth and mildew formation. Sincethey are exceptionally nonphytotoxic, they may be applied safely to awide variety of plants. Some of the additional parent materials to whichthey may be applied for protective purposes are leather, wood, fur,wcol, coated fabrics, and other substances.

They may be reduced to an impalpable powder and applied as an undiluteddust or mixed with a solid carrier, such as clay, talc, and bentcnite,as well as other carriers known in the art (see Frear Chemistry ofInsecticides, Fungicides and Herbicides). They may thus be applied as aspray in a liquid carrier, either as a solution in a solvent, or as asuspension in a non-solvent, such as water. When applied as a spray inwater, it may be desirable to incorporate wetting agents.

The N-thiotrichloromethyl morpholine compound of this invention ingeneral is soluble to a small extent in organic solvents such asacetone, ethyl alcohol, benzene, naphtha, chlorinated solvents, etc.

The water-soluble wetting agents that may be used in aqueous emulsionscomprise the sulfates of long-chain alcohols such as dodecanol up tooctadecanol, sulfonated amide and ester derivatives, sulfonatedaromatics, and mixed alkylaryl sulfonate derivatives, esters of fattyacids such as the ricinoleic acid ester of sorbitol, and petroleumsulfonates of C10 to C20 length.

ill

The non-ionic emulsifying agents such as the ethylene oxide condensationproducts of alkylated phenols may also be used. It is to be understoodthat these non-ionic emulsifying agents such as the ethylene oxidecondensation products of alkylated phenols may also be used. It is to beunderstood that these and similar compounds are intended when the termwetting agent is used hereafter.

The compounds of this invention may also be admixed with carriers thatare themselves active, such as other parasiticides, hormones,herbicides, fertilizers and wetting agents. Stomach and contactinsecticides such as the arsenates, fluorides, rotenone, and the variousfish poisons and organic insecticides, such asdi(p-)chlorophenyltrichloroethane, benzene-hexachloride, and similarproducts may also be advantageously added.

This invention has been described with respect to preferred embodimentsbut is not intended to be limited thereby.

What is claimed is:

1. As a new chemical compound, N-thiotrichloromethyl morpholinecorresponding to the formula:

enters o \NSC c1;

onio 2 2. A fungicidal dust composition comprising N-thiotrichloromethylmorpholine corresponding to the formula:

CHzCHz NSC C13 CHr-C z admixed with a powdered clay.

3. A fungicidal dust composition as in claim 2 in which the clay isbentonite.

4. A fungicidal composition containing N- thiotrichloromethyl morpholinecorresponding to the formula:

OHg- CHz /NSCC13 GHQ-CH2 as the active ingredient admixed with asurfaceactive dispersing agent which lowers the surface tension of waterand thereby promotes aqueous colloidal dispersions of theN-thiotrichloromethyl morpholine.

5. A fungicidal composition as in claim 4 in which the dispersing agentis a surface tension reducing agent for water selected from the groupconsisting of long-chain alcohol sulfates, sulfonated amide derivatives,sulfonated ester derivatives, sulfonated aromatic derivatives,sulfonated alkyl-aryl derivatives and petroleum sulfonates of C10 to C20length.

6. A fungicidal composition comprising N- thiotrichloromethyl morpholinecorresponding to the formula:

GHQ-0H2 Nso 013 onrcnz as the active ingredient dissolved in a solventtherefor.

7. A fungicidal composition comprising N- thiotrichloromethyl morpholinecorresponding to the formula:

95 the active ingredient admixed with a solid, powdered inert diluent.

8. A fungicidal composition comprising as the active ingredientN-thiotrichloromethyl morpholine corresponding to the formula:

OH -CH; O NSC Ola contained in an aqueous emulsion with a wetting agent.

ROGER S. HAWLEY.

6 REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date Re.19,286 Zaucker et a1. Aug. 21,1934 2,045,888 Tschunkur et a1. June 30, 1936 2,439,734 I-Iimel et a1.Apr. 13, 1948 OTHER REFERENCES Ingram et a1., Jour. Amer. Chem. Soc,(1942), vol. 64 pp. 2506-2507.

1. AS A NEW CHEMICAL COMPOUND, N-THIOTRICHLOROMETHYL MORPHOLINECORRESPONDING TO THE FORMULA: